Compression thermodynamics

Pressure-area ( r(A)) isotherms Phase transitions, packing densities, compressibilities, thermodynamic cheiracteristics. Molecular Interpretation very limited. 

These two instruments are designed to compensate for mercury compressibility thermodynamically by balancing the slight expansion due to compressive heating and the associated change in the hydraulic oil dielectric value with pressure. A cell filled with mercury will indicate a deviation on the volume axis of less than 0.5% of full scale therefore there is no need for a blank run. 

The critical pressure, critical molar volume, and critical temperature are the values of the pressure, molar volume, and thermodynamic temperature at which the densities of coexisting liquid and gaseous phases just become identical. At this critical point, the critical compressibility factor, Z, is ... 

Figure 4.14 Behavior of thermodynamic variables at Tg for a second-order phase transition (a) volume and fb) coefficient of thermal expansion a and isothermal compressibility p.

By an assortment of thermodynamic manipulations, the quantities dn/dp and [N (d G/dp )o] can be eliminated from Eq. (10.48) and replaced by the measurable quantities a, /3, and dn/dT the coefficients of thermal expansion, isothermal compressibility, and the temperature coefficient of refractive index, respectively. With these substitutions, Eq. (10.48) becomes... 

Rankine Cycle Thermodynamics. Carnot cycles provide the highest theoretical efficiency possible, but these are entirely gas phase. A drawback to a Carnot cycle is the need for gas compression. Producing efficient, large-volume compressors has been such a problem that combustion turbines and jet engines were not practical until the late 1940s. 

Although modeling of supercritical phase behavior can sometimes be done using relatively simple thermodynamics, this is not the norm. Especially in the region of the critical point, extreme nonideahties occur and high compressibilities must be addressed. Several review papers and books discuss modeling of systems comprised of supercritical fluids and soHd orHquid solutes (rl,i4—r7,r9,i49,r50). 

Gas AntisolventRecrystallizations. A limitation to the RESS process can be the low solubihty in the supercritical fluid. This is especially evident in polymer—supercritical fluid systems. In a novel process, sometimes termed gas antisolvent (GAS), a compressed fluid such as CO2 can be rapidly added to a solution of a crystalline soHd dissolved in an organic solvent (114). Carbon dioxide and most organic solvents exhibit full miscibility, whereas in this case the soHd solutes had limited solubihty in CO2. Thus, CO2 acts as an antisolvent to precipitate soHd crystals. Using C02 s adjustable solvent strength, the particle size and size distribution of final crystals may be finely controlled. Examples of GAS studies include the formation of monodisperse particles (<1 fiva) of a difficult-to-comminute explosive (114) recrystallization of -carotene and acetaminophen (86) salt nucleation and growth in supercritical water (115) and a study of the molecular thermodynamics of the GAS crystallization process (21). 

Other Refrigeration Methods. Cryocoolers provide low temperature refrigeration on a smaller scale by a variety of thermodynamic cycles. The Stirling cycle foUows a path of isothermal compression, heat transfer to a regenerator matrix at constant volume, isothermal expansion with heat transfer from the external load at the refrigerator temperature, and finally heat transfer to the fluid from the regenerator at constant volume. 

TABLE 2-354 Thermodynamic Properties of Compressed Steam Concluded)... 

Calculation of Actual Work of Compression For simplicity, the work of compression is calciilated by the equation for an ideal gas in a three-stage reciprocating machine with complete intercoohng and with isentropic compression in each stage. The work so calculated is assumed to represent 80 percent of the actual work. The following equation may be found in any number of textbooks on thermodynamics ... 

Flows are typically considered compressible when the density varies by more than 5 to 10 percent. In practice compressible flows are normally limited to gases, supercritical fluids, and multiphase flows containing gases. Liquid flows are normally considerea incompressible, except for certain calculations involved in hydraulie transient analysis (see following) where compressibility effects are important even for nearly incompressible hquids with extremely small density variations. Textbooks on compressible gas flow include Shapiro Dynamics and Thermodynamics of Compre.ssible Fluid Flow, vol. 1 and 11, Ronald Press, New York [1953]) and Zucrow and Hofmann (G .s Dynamics, vol. 1 and 11, Wiley, New York [1976]). 

With flashes carried out along the appropriate thermodynamic paths, the formalism of Eqs. (6-139) through (6-143) applies to all homogeneous equihbrium compressible flows, including, for example, flashing flow, ideal gas flow, and nonideal gas flow. Equation (6-118), for example, is a special case of Eq. (6-141) where the quahty x = and the vapor phase is a perfect gas. 

Although the T-s diagram is veiy useful for thermodynamic analysis, the pressure enthalpy diagram is used much more in refrigeration practice due to the fact that both evaporation and condensation are isobaric processes so that heat exchanged is equal to enthalpy difference A( = Ah. For the ideal, isentropic compression, the work could be also presented as enthalpy difference AW = Ah. The vapor compression cycle (Ranldne) is presented in Fig. H-73 in p-h coordinates. 

Thermocompression Evaporators Thermocompression-evap-orator calculations [Pridgeon, Chem. Metall. Eng., 28, 1109 (1923) Peter, Chimin Switzerland), 3, II4 (1949) Petzold, Chem. Ing. Tech., 22, 147 (1950) and Weimer, Dolf, and Austin, Chem. Eng. Prog., 76(11), 78 (1980)] are much the same as single-effect calculations with the added comphcation that the heat suppied to the evaporator from compressed vapor and other sources must exactly balance the heat requirements. Some knowledge of compressor efficiency is also required. Large axial-flow machines on the order of 236-mVs (500,000-ftVmin) capacity may have efficiencies of 80 to 85 percent. Efficiency drops to about 75 percent for a I4-mVs (30,000-ftVmin) centrifugal compressor. Steam-jet compressors have thermodynamic efficiencies on the order of only 25 to 30 percent. 

The thermal efficiency of the process (QE) should be compared with a thermodynamically ideal Carnot cycle, which can be done by comparing the respective indicator diagrams. These show the variation of temperamre, volume and pressure in the combustion chamber during the operating cycle. In the Carnot cycle one mole of gas is subjected to alternate isothermal and adiabatic compression or expansion at two temperatures. By die first law of thermodynamics the isothermal work done on (compression) or by the gas (expansion) is accompanied by the absorption or evolution of heat (Figure 2.2). 

The jump conditions must be satisfied by a steady compression wave, but cannot be used by themselves to predict the behavior of a specific material under shock loading. For that, another equation is needed to independently relate pressure (more generally, the normal stress) to the density (or strain). This equation is a property of the material itself, and every material has its own unique description. When the material behind the shock wave is a uniform, equilibrium state, the equation that is used is the material s thermodynamic equation of state. A more general expression, which can include time-dependent and nonequilibrium behavior, is called the constitutive equation. 

Thermodynamic Effects of Shock Compression and the Hugoniot Curve... 

Constitutive relation An equation that relates the initial state to the final state of a material undergoing shock compression. This equation is a property of the material and distinguishes one material from another. In general it can be rate-dependent. It is combined with the jump conditions to yield the Hugoniot curve which is also material-dependent. The equation of state of a material is a constitutive equation for which the initial and final states are in thermodynamic equilibrium, and there are no rate-dependent variables. 

Figure 4.2. Pressure-volume compression curves. For isentrope and isotherm, the thermodynamic path coincides with the locus of states, whereas for shock, the thermodynamic path is a straight line to point Pj, V, on the Hugoniot curve, which is the locus of shock states.

Adadurov, G.A. and Gol danskii, V.I., Transformations of Condensed Substances Under Shock-Wave Compression in Controlled Thermodynamic Conditions, Russian Chem. Rev. 50 (10), 848-957 (1981). 

There is a Second Law thermodynamic advantage in operating an expander at as low a temperamre as possible. In most applications it has been aiTanged to discharge just above tlie dew point of tlie expanded gas. If the cold compressed gas could enter tlie expander at or near its dew point, the expander would then operate condensing and at the lowest possible temperamre. Such condensate has traditionally been troublesome in turbines, but tliis has been solved in modern turboexpanders. 

---